The nature of the surface film on steel treated with cerium and lanthanum cinnamate based corrosion inhibitors

The corrosion inhibition mechanisms of new cerium and lanthanum cinnamate based compounds have been investigated through the surface characterisation of the steel exposed to NaCl solution of neutral pH. Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy was used to identify the nature of the deposits on the metal surface and demonstrated that after accelerated tests the corrosion product commonly observed on steel (i.e. lepidocrocite, γ-FeOOH) is absent. The cinnamate species were clearly present on the steel surface upon exposure to NaCl solution for short periods and appeared to coordinate through the iron. At longer times the Rare Earth Metal (REM) oxyhydroxide species are proposed to form as identified through the bands in the 1400–1500 cm⁻¹ region. These latter bands have been previously assigned to carbonate species adsorbed onto REM oxyhydroxide surfaces. The protection mechanism appears to involve the adsorption of the REM–cinnamate complex followed by the hydrolysis of the REM to form a barrier oxide on the steel surface.

Potentiostatic control of ionic liquid surface film formation on ZE41 magnesium alloy

The generation of potentially corrosion-resistant films on light metal alloys of magnesium have been investigated. Magnesium alloy, ZE41 [Mg−Zn−Rare Earth (RE)-Zr, nominal composition 4 wt % Zn, 1.7 wt % RE (Ce), 0.6 wt % Zr, remaining balance, Mg], was exposed under potentiostatic control to the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate, denoted [P_6,6,6,14][DPP]. During exposure to this IL, a bias potential, shifted from open circuit, was applied to the ZE41 surface. Electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) were used to monitor the evolution of film formation on the metal surface during exposure. The EIS data indicate that, of the four bias potentials examined, applying a potential of −200 mV versus OCP during the exposure period resulted in surface films of greatest resistance. Both EIS measurements and scanning electron microscopy (SEM) imaging indicate that these surfaces are substantially different to those formed without potential bias. Time of flight-secondary ion mass spectrometry (ToF-SIMS) elemental mapping of the films was utilized to ascertain the distribution of the ionic liquid cationic and anionic species relative to the microstructural surface features of ZE41 and indicated a more uniform distribution compared with the surface following exposure in the absence of a bias potential. Immersion of the treated ZE41 specimens in a chloride contaminated salt solution clearly indicated that the ionic liquid generated surface films offered significant protection against pitting corrosion, although the intermetallics were still insufficiently protected by the IL and hence favored intergranular corrosion processes.

The effect of treatment time on the ionic liquid surface film formation: promising surface coating for Mg alloy AZ31

Mg alloys are attractive materials for medical devices. The main limitation is that they are prone to corrosion. A low toxicity surface coating that enables uniform, controlled corrosion at a desired rate (this usually means it must offer barrier functions for a limited time period) is desirable. Phosphate-based ionic liquids (ILs) are known to induce a coating that can reduce the corrosion rate of Mg alloys, Furthermore, some ILs are known to be biocompatible and therefore, controlling the corrosion behaviour of an Mg alloy and its surface biocompatibility can be achieved through adding an appropriate low toxic IL surface layer to the substrate. In this study, we have evaluated the cytotoxicity of three phosphate-based ILs to primary human coronary artery endothelial cells. Among them, tributyl(methyl)-phosphonium diphenylphosphate (P1,4,4,4dpp) shows the lowest cytotoxicity. Therefore, further work was aimed at developing an appropriate treatment method to produce a homogeneous and passive surface coating based on P1,4,4,4dpp IL, with the focus on investigating the effect of treatment time. The results showed that that the formation of IL coating on AZ31 has proceeded progressively, and treatment time plays an important role. An IL treatment at 100 °C with an extended treatment time of 5 h significantly enhanced corrosion resistance of the AZ31 alloy in simulated body fluid. Additionally, the corrosion morphology was uniform and there was no evidence of "localized pitting corrosion" observed. Such a performance makes this ionic liquid coating as a potential surface coating biodegradable Mg-based implants.

New insights into the fundamental chemical nature of ionic liquid film formation on magnesium alloy surfaces

Ionic liquids (ILs) based on trihexyltetradecylphosphonium coupled with either diphenylphosphate or bis(trifluoromethanesulfonyl)amide have been shown to react with magnesium alloy surfaces, leading to the formation a surface film that can improve the corrosion resistance of the alloy. The morphology and microstructure of the magnesium surface seems critical in determining the nature of the interphase, with grain boundary phases and intermetallics within the grain, rich in zirconium and zinc, showing almost no interaction with the IL and thereby resulting in a heterogeneous surface film. This has been explained, on the basis of solid-state NMR evidence, as being due to the extremely low reactivity of the native oxide films on the intermetallics (ZrO₂ and ZnO) with the IL as compared with the magnesium-rich matrix where a magnesium hydroxide and/or carbonate inorganic surface is likely. Solid-state NMR characterization of the ZE41 alloy surface treated with the IL based on (Tf)₂N− indicates that this anion reacts to form a metal fluoride rich surface in addition to an organic component. The diphenylphosphate anion also seems to undergo an additional chemical process on the metal surface, indicating that film formation on the metal is not a simple chemical interaction between the components of the IL and the substrate but may involve electrochemical processes.

The effect of potential bias on the formation of ionic liquid generated surface films on Mg alloys

An electrochemical approach to the formation of a protective surface film on Mg alloys immersed in the ionic liquid (IL), trihexyl(tetradecyl)phosphonium–bis 2,4,4-trimethylpentylphosphinate, was investigated in this work. Initially, cyclic voltammetry was used with the Mg alloy being cycled from OCP to more anodic potentials. EIS data indicate that, under these circumstances, an optimum level of protection was achieved at intermediate potentials (e.g., 0 or 0.25 V versus Ag/AgCl). In the second part of this paper, a small constant bias was applied to the Mg alloy immersed in the IL for extended periods using a novel cell design. This electrochemical cell allowed us to monitor in situ surface film formation on the metal surface as well as the subsequent corrosion behaviour of the metal in a corrosive medium. This apparatus was used to investigate the evolution of the surface film on an AZ31 magnesium alloy under a potential bias (between ±100 mV versus open circuit) applied for over 24 h, and the film evolution was monitored using electrochemical impedance spectroscopy (EIS). A film resistance was determined from the EIS data and it was shown that this increased substantially during the first few hours (independent of the bias potential used) with a subsequent decrease upon longer exposure of the surface to the IL. Preliminary characterization of the film formed on the Mg alloy surface using ToF-SIMS indicates that a multilayer surface exists with a phosphorous rich outer layer and a native oxide/hydroxide film underlying this. The corrosion performance of a treated AZ31 specimen when exposed to 0.1 M NaCl aqueous solution showed considerable improvement, consistent with electrochemical data.

Film formation in trihexyl(tetradecyl)phosphonium diphenylphosphate ([P6,6,6,14][dpp]) ionic liquid on AA5083 aluminium alloy

Whilst ionic liquids (IL) have been shown to inhibit corrosion on some reactive metals and alloys by forming a surface film, e.g. Li and Mg, understanding of the interaction between ionic liquids and aluminium is lacking. This research study investigated the viability of film formation on AA5083 Aluminium Alloy by electrochemical treatments in the trihexyl(tetradecyl)phosphonium diphenylphosphate ([P6,6,6,14][dpp]) IL. Two-step anodic treatments were performed on AA5083 in the IL, followed by a comparison of the corrosion behaviour of the IL-treated samples with that of a control. It has been revealed that the two-step IL-treatment led to reduced current densities on AA5083 under cyclic voltammetry scan in the IL before and after the IL-treatment. Lower corrosion rates have been shown on all samples treated in IL at room temperature. Surface characterisation showed a non-uniform porous film on the 50°C IL-treated sample with a film thickness ranging between 37nm and 155nm. The IL-film enhanced the corrosion resistance of AA5083 by protecting the Al-matrix and Fe-rich intermetallic particles (IMPs). Although findings of this study suggest similar IL-film formation as that on Li and Mg, more research needs to be conducted to optimise the electrochemical treatment conditions and ultimately to develop a robust IL-film formation procedure for corrosion protection.

Exploring corrosion protection of Mg via ionic liquid pretreatment

We present the development of a 10–100 nanometer thick surface film upon pure Mg on exposure to an ionic liquid (IL) based on the bis(trifluoromethanesulfonyl)amide (TFSA) anion. This film formation is the result of the oxidative reactivity of the metal in the IL, with the subsequent effect of ultimately protecting the underlying metal from corrosion in aqueous chloride containing solution. Film formation was studied in the IL using an electrochemical droplet cell. It was seen that this film is adherent and subsequently facilitates appreciable protection against corrosion as judged by subsequent electrochemical testing in the form of potentiodynamic polarization and impedance spectroscopy, along with direct observation. The physical film morphology was studied by electron microscopy and focused ion beam.

Phosphonium ionic liquids as lubricants for aluminium-steel

The performance of a series of novel room temperature ionic liquids (ILs) based on the trihexyl(tetradecyl)phosphoniumcation (P66614 +) and a number of novel anions have been studied in pin-on-disk tests using a 100Cr6 steel ball on AA2024 aluminium disks.

The anions coupled to the (P66614 +) cation include diphenyl phosphate (DPP-), dibutyl phosphate (DBP-), bis (2,4,4-trimethyl pentyl) phosphinate (M3PPh-) and bis(2-ethyl hexyl) phosphate (BEH-).

More traditional anions such as bis(trifluoromethanesulfonyl) amide (NTf2 -) and bromide (Br-) were also investigated. Experiments were conducted at various loads to assess the IL film forming abilities.

The results suggest that the structure of the anion is important in forming a surface film that reduces the friction and wear of the aluminium disk. At 30N five of the six ILs tested showed a 30-90% reduction in wear, as determined from wear scar depth measurements, compared to fully formulated diesel oil.

The IL lubricant with a diphenyl phosphate anion achieved the lowest wear coefficient, showing a better performance than a typical fluorine-containing IL anion, NTf2.

To further investigate wear mechanisms and surface interactions the wear scars were analysed using a scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS).

Clinical evaluation of long-term users of two contact lens care preservative systems

Purpose: To clinically evaluate long-term users of two different contact lens care preservative systems and to investigate whether prolonged use is associated with an increase in the prevalence of dry eye.

Methods: Eighty-nine wearers of group IV hydrogel or silicone hydrogel lenses participated in this one-visit, investigator-masked study. Subjects were required to have consistently used a polyhexamethylene biguanide (PHMB) or polyquaternium-1 (PQT) based solution for 2 years. Consistent use was defined as 80% for the past 2 years and 100% for the past year. Clinical assessments included: average and comfortable wear time; overall and end-of-day comfort; signs of dryness, discomfort, burning or stinging, grittiness or scratchiness and visual changes; non-invasive and fluorescein break-up-time; pre-ocular tear film lipids, tear meniscus height, Schirmer and fluorescein clearance tests; limbal and bulbar hyperemia; palpebral roughness; corneal and conjunctival staining; lens front surface wetting; and lens film deposits.

Results: Significantly more grittiness or scratchiness was reported by subjects using a PHMB-containing system (67% vs. 44%; P = 0.02). Palpebral roughness and hyperemia were significantly greater in the PHMB group wearing group IV lenses (P = 0.01 and P = 0.05, respectively). Corneal staining was significantly higher in the PHMB users in all four peripheral sectors (P < 0.01). Nasal and temporal conjunctival staining was also significantly higher for users of PHMB-containing systems (P < 0.05). Front surface lens wettability was significantly better for group IV PQT users compared to PHMB users (P = 0.008), with 84% vs. 72%, respectively, with lenses graded by the investigator as having good or excellent wettability. Significantly higher levels of lens front surface film deposits were noted with PHMB users (P = 0.007), with 58% of group IV lenses treated with PHMB compared with 38% of group IV lenses treated with PQT showing some lens front surface film deposition. No significant differences between the two preservative system groups were noted for the range of dry eye evaluations nor the remaining clinical assessments.

Conclusions: Differences in both ocular and lens characteristic were observed between long-term users of two preservative systems used in many contact lens multi-purpose solutions. The findings from this study did not support the hypothesis that prolonged use of PHMB-containing solutions leads to dry eye. Additional studies including a larger sample size and perhaps longer use of the systems could help to further elucidate differences in clinical performance between systems.

The corrosion inhibition of aluminium alloy 7075-T651 with cerium and Mischmetal di phenyl phosphate

Previous studies have shown that cerium diphenyl phosphate (Cedpp) 3 is a very effective inhibitor of corrosion of aluminium alloys in chloride solutions. This paper describes the results of further studies using electrochemical and constant immersion corrosion tests to compare the effectiveness of Ce(dpp) 3 and Mischmetal diphenyl phosphate Mm(dpp) 3 as inhibitors of corrosion pitting on AA7075-T651 aluminium alloy. The results shows that both Ce(dpp) 3 and Mm(dpp) 3 are excellent inhibitors of pitting corrosion of this alloy in very aggressive environments of continuously aerated 0.1M and 1.0M sodium chloride (NaCl) solutions. Polarisation tests indicate that these compounds act as a cathodic inhibitors by reducing the rate of the oxygen reduction reaction, which results in a decreased corrosion current density and a separation of the corrosion potential from the pitting potential. This inhibition is thought to be due to the formation of a surface film consisting of rare earth metal oxide, aluminium oxide and a cerium-aluminium organo-phosphate complex. Surface analysis data from scanning electron microscopy and X-ray Energy Dispersive Spectroscopy show the complex nature of this protective film. This work further develops our understanding about the mechanisms through which these complex films form, and how inhibition occurs in the presence of these compounds.

Corrosion of mg alloy ZE41 and its mitigation using ionic liquids

Magnesium alloy ZE41 (Mg-Zn-RE-Zr), which is used extensively in the aerospace industry, possesses excellent mechanical properties albeit poor corrosion resistance. This work investigates the mechanism of corrosion, and the interaction between the grain boundary intermetallic phases, the zirconium (Zr)-rich regions within the grains and the bulk Mg rich matrix in both the as-cast and heat-treated conditions. The results of optical and scanning electron microscopy (SEM) show the importance of the microstructure in the initiation and propagation of corrosion in an aqueous environment. The Zr-rich regions play a distinct role in the early stages of corrosion with this alloy. The second part of this work investigates the interaction of two different ionic liquids (ILs) with the surface of the ZE41 alloy. ILs based on trihexyltetradecylphosphonium (P 6,6,6,14) coupled with either diphenylphosphate (DPP) or bis(trifluoromethanesulfonyl) amide (Tf 2N) have been shown to react with Mg alloy surfaces, leading to the formation of a surface film that can improve the corrosion resistance of the alloy. The interaction of the ILs with the ZE41 surface has been investigated by optical microscopy and SEM. Surface characterization has been performed using Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS). The surface characterization and microscopy revealed the preferential interaction with the grain boundaries and grain boundary phases. Thus the morphology and microstructure of the Mg surface seems critical in determining the nature of the interaction with the IL. The corrosion protection of the IL films formed on the ZE41 surface was investigated by SEM and potentiodynamic polarisation.

The behaviour of praseodymium 4-hydroxycinnamate as an inhibitor for carbon dioxide corrosion and oxygen corrosion of steel in NaCl solutions

Praseodymium 4-hydroxycinnamate (Pr(4OHCin)3) was investigated as a novel corrosion inhibitor for steel in NaCl solutions, and found to be effective at inhibiting corrosion in both CO2-containing and naturally-aerated systems. Surface analysis results suggest that the corrosion inhibition ability of Pr(4OHCin)3 in the naturally-aerated corrosion system could be attributed to the formation of a continuous protective film. For the CO2-containing system, the corrosion inhibition efficiency of Pr(4OHCin)3 was predominantly because of formation of protective inhibiting deposits at the active electrochemical corrosion sites, in addition to a thinner surface film deposit. © 2013.

Novel imidazolinium ionic liquids and organic salts

The preparation and physical properties of a novel family of ionic liquids and organic salts based on the imidazolinium cation are described, and compared with their imidazolium analogues in some cases. Ionic liquids were obtained with the triflate, formate and salicylate anions, while > 100 °C melting points were observed with acetate and several other benzoate derivatives. The triflate salt was less ion-conductive than the corresponding imidazolium salt, but less so than expected on the basis of its viscosity, suggesting a contribution from proton conductivity. The electrochemical window of the imidazolinium was slightly extended in the reductive direction, due to the lower proton activity produced by the cation in this case. Imidazolinium salts are also known to exhibit anti-corrosion properties and hence a preliminary study of this property is also reported; 2-methylimidazolinium 4-hydroxycinnamate was found to show strong anodic corrosion inhibition on mild steel.